TWI480365B - Flame retardant hardener and flame retardant hardene composition - Google Patents
Flame retardant hardener and flame retardant hardene composition Download PDFInfo
- Publication number
- TWI480365B TWI480365B TW100117823A TW100117823A TWI480365B TW I480365 B TWI480365 B TW I480365B TW 100117823 A TW100117823 A TW 100117823A TW 100117823 A TW100117823 A TW 100117823A TW I480365 B TWI480365 B TW I480365B
- Authority
- TW
- Taiwan
- Prior art keywords
- flame
- hardener
- flame retardant
- temperature
- phosphorus
- Prior art date
Links
Description
本發明提供一種耐燃性硬化劑及耐燃性硬化劑組成物，係用於製造黏合片、複合材料、積層板、印刷電路板、增厚法之基板、銅箔用之接著劑、預浸漬片等。 The present invention provides a flame-retardant hardener and a flame-resistant hardener composition, which are used for producing an adhesive sheet, a composite material, a laminate, a printed circuit board, a substrate for a thickening method, an adhesive for a copper foil, a prepreg, etc. .
近年來國際大廠規範、歐盟指令等環保要求，鹵素耐燃劑將會逐漸被淘汰，這是由於鹵素在受熱過程中會分解釋放出具有腐蝕性的鹵化氫氣體及大量煙霧，雖然可以達到預期的耐燃效果，但是卻會危害人體健康及臭氧層破壞，以其它耐燃元素取代鹵素所發展出新型難燃劑，是近年來全球耐燃劑發展之趨勢。 In recent years, international environmental standards, EU directives and other environmental requirements, halogen flame retardants will gradually be eliminated, because halogens will decompose during the heating process to release corrosive hydrogen halide gas and a large amount of smoke, although it can achieve the expected It is a flame retardant effect, but it will endanger human health and the destruction of the ozone layer. The replacement of halogen with other flame-resistant elements has developed a new flame retardant, which is the trend of global flame retardant development in recent years.
磷系化合物做為新一代具有環保概念的難燃劑，已被廣泛地研究和應用，例如直接以磷酸酯等來取代鹵素之耐燃劑，以改善樹脂燃燒特性，然而添加這些磷化合物在樹脂中，會造成磷化合物在樹脂中移行性或劣解，磷化合物的高溫高溼水解問題，直接影響到樹脂基材的電氣性質、力學特性。 Phosphorus compounds have been widely studied and applied as a new generation of environmentally friendly flame retardants. For example, halogen-based flame retardants are directly substituted by phosphates to improve the combustion characteristics of resins. However, these phosphorus compounds are added in the resin. It causes the migration or inferior solution of the phosphorus compound in the resin, and the high-temperature and high-humidity hydrolysis of the phosphorus compound directly affects the electrical properties and mechanical properties of the resin substrate.
因環保與安全實用考量，反應型磷系難燃劑已逐漸取得市場主流地位，其中以9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(9,10-Dihydro-9-oxa-10-phosphaphanthrene-10-oxide/簡稱DOPO)最為重要，在印刷電路板走入無鹵化後，DOPO型環氧樹脂因含有DOPO剛性基，使得DOPO型環氧樹脂比傳統TBBA型溴系環氧樹脂更具脆性，在印刷電路板 加工過程中因裁邊、鑽孔等外力，造成不規則龜裂現象，使得製成良率無法提高。 Due to environmental and safety considerations, reactive phosphorus-based flame retardants have gradually gained market mainstream status, including 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10- Dihydro-9-oxa-10-phosphaphanthrene-10-oxide/DOPO is the most important. After the printed circuit board is halogen-free, DOPO-type epoxy resin contains DOPO rigid base, making DOPO epoxy resin more traditional than TBBA. Type bromine epoxy resin is more brittle on printed circuit boards During the processing, due to external forces such as trimming and drilling, irregular cracking is caused, and the yield can not be improved.
中華民國專利公告476771號揭示一種含磷難燃環氧樹脂組成物中之含磷化合物，該含磷化合物部份係為雙酚A或雙酚與甲醛、DOPO之反應物縮合而成，可做為含磷硬化劑使用；其缺點在於其中之合成方法其反應率低、DOPO殘存量高、其與環氧樹脂固化物吸水性高，不利於用於電子材料之用途。 The Republic of China Patent Publication No. 476771 discloses a phosphorus-containing compound in a phosphorus-containing flame-retardant epoxy resin composition, which is obtained by condensing a reaction of bisphenol A or bisphenol with formaldehyde and DOPO. It is used as a phosphorus-containing hardener; its disadvantage is that the synthesis method has a low reaction rate, high DOPO residual amount, and high water absorption with the epoxy resin cured product, which is disadvantageous for use in electronic materials.
中華民國專利公開200604239號揭示一種含磷化合物之製造方法，包含使下述反應：(A)至少具有選自H-P=O基、PH基及P-OH基之基之有機磷化物及(B)酚醛烷基醚樹脂；其缺點在於其環氧樹脂半固化物之固化玻璃轉移溫度，會隨半固化物存放時間而下降，及其環氧樹脂固化物之磷含量需要3.0%以上才會達到UL-94/V-0耐燃效果。 The Republic of China Patent Publication No. 200604239 discloses a method for producing a phosphorus-containing compound comprising the following reaction: (A) an organic phosphide having at least a group selected from the group consisting of HP=O group, PH group and P-OH group, and (B) Phenolic alkyl ether resin; its disadvantage is that the curing glass transition temperature of the epoxy resin semi-cured product will decrease with the semi-cured material storage time, and the phosphorus content of the epoxy resin cured product needs to be more than 3.0% to reach UL -94/V-0 flame resistance.
中華民國專利公開201109371A1號揭示一種製造具有阻燃性及耐熱性經磷改質之阻燃硬化劑之方法，其包含1).將酚化合物及醛化合物在鹼性催化劑存在下反應，以製備一可溶酚醛樹脂化合物；及2).將該經製備之可溶酚醛樹脂化合物與一含磷化合物於溶劑導引脫水，以便形成該經磷改質的阻燃硬化劑；其缺點在於其環氧樹脂半固化物之固化玻璃轉移溫度，會隨半固化物存放時間而下降，及其環氧樹脂固化物之磷含量需要3.0%以上才會達到UL-94/V-0耐燃效果。 The Republic of China Patent Publication No. 201109371A1 discloses a method for producing a flame retardant and heat-resistant phosphorus-modified flame retardant hardener comprising 1) reacting a phenol compound and an aldehyde compound in the presence of a basic catalyst to prepare a a resol resin compound; and 2). The prepared resol resin compound and a phosphorus-containing compound are dehydrated in a solvent to form the phosphorus-modified flame retardant hardener; The curing glass transition temperature of the resin semi-cured material decreases with the semi-cured material storage time, and the phosphorus content of the epoxy resin cured product needs to be more than 3.0% to achieve the UL-94/V-0 flame resistance effect.
由以上可知目前所揭示之含磷硬化劑，應用在印刷電路板 上，雖然克服了加工過程中因裁邊、鑽孔等外力所造成不規則龜裂問題，但仍存在其環氧樹脂半固化物之固化玻璃轉移溫度，會隨半固化物存放時間而下降問題，及其環氧樹脂固化物之磷含量需要3.0%以上才會達到UL-94/V-0耐燃效果。 From the above, the presently disclosed phosphorus-containing hardener is applied to a printed circuit board. Although it overcomes the irregular cracking caused by external forces such as trimming and drilling during the processing, there is still a problem that the curing glass transition temperature of the epoxy resin semi-cured material will decrease with the storage time of the semi-cured material. , and the epoxy content of the epoxy resin cured product needs to be more than 3.0% to achieve the UL-94/V-0 flame resistance effect.
發明所欲解決之問題，如目前公知技術範圍之含磷硬化劑，其存在的問題為，先前技術之含磷硬化劑與環氧樹脂半固化物之固化玻璃轉移溫度，會隨半固化物存放時間而下降；其被忽略的問題為，含磷硬化劑與環氧樹脂固化物之磷含量需要3.0%以上才會達到UL-94/V-0耐燃效果。 The problem to be solved by the invention, such as the phosphorus-containing hardener of the prior art, has the problem that the curing glass transition temperature of the prior art phosphorus-containing hardener and epoxy resin semi-cured material is stored with the semi-cured material. The time is down; the neglected problem is that the phosphorus content of the phosphorus-containing hardener and the epoxy resin cured product needs to be more than 3.0% to achieve the UL-94/V-0 flame resistance effect.
解決之問題之技術手段，鑑於上述問題，本發明提供一種耐燃性硬化劑，其具有如式(一)所示之化學結構：
本發明之一種耐燃性硬化劑組成物，包括：(a)耐燃性硬化劑，其具有如式(一)所式之化學結構；(b)環氧樹脂；(c)硬化促進劑。 A flame resistant hardener composition of the present invention comprises: (a) a flame retardant hardener having a chemical structure of the formula (I); (b) an epoxy resin; and (c) a hardening accelerator.
對照先前技術之功效，先前技術之含磷硬化劑，雖然在產業上已被大量使用，但對於高玻璃轉移溫度之需求仍有不足，半固 化物之固化玻璃轉移溫度，有經時性玻璃轉移溫度下降等問題仍待解決。 Compared with the efficacy of the prior art, the prior art phosphorus-containing hardener, although widely used in the industry, still lacks the demand for high glass transition temperature, semi-solid The problem of the solidification glass transition temperature of the compound, the temperature transition of the glass transition with time, etc. remains to be solved.
本發明之一種耐燃性硬化劑，其含有磷及特殊阻燃性結構，可以再包含氮，可以有效降低達到UL-94/V-0所需之磷含量，減少對原有物性的破壞，提高玻璃轉移溫度，避免半固化物之固化玻璃轉移溫度經時下降，為先前技術之含磷硬化劑所不及，可以符合產業殷切之需求。 The flame-retardant hardener of the invention contains phosphorus and a special flame-retardant structure, and can further contain nitrogen, can effectively reduce the phosphorus content required to reach UL-94/V-0, reduce the damage to the original physical properties, and improve The glass transfer temperature prevents the solidification glass transition temperature of the semi-cured material from decreasing over time, which is inferior to the prior art phosphorus-containing hardener, and can meet the demand of the industry.
本發明之目的在提供一種耐燃性硬化劑，其具有如式(一)所示之化學結構：
本發明之一種耐燃性硬化劑，其特徵在於分子鏈具有如式(二)所示之化學結構：
本發明合成一種耐燃性硬化劑，其所使用之二酚類包括：
本發明合成一種耐燃性硬化劑，其所使用之三嗪類包括：三聚氰胺、甲基胍胺、苯基胍胺、胍胺衍生物、三聚氰酸、甲基三聚氰酸酯、乙基三聚氰酸酯、乙醯基三聚氰酸酯、三聚氰酸衍生物等。 The invention synthesizes a flame retardant hardener, and the triazines used thereof include: melamine, methyl decylamine, phenyl decylamine, decylamine derivative, cyanuric acid, methyl cyanurate, ethyl Cyanuric acid ester, acetyl phthalocyanate, cyanuric acid derivative, and the like.
本發明合成一種耐燃性硬化劑，其所使用之溶劑包括：苯、甲苯、二甲苯、二噁烷、DMF、DMAC、甲醇、乙醇、丙醇、丁醇、二丙二醇甲醚、二乙二醇甲醚、丙二醇甲醚、乙二醇甲醚、丙二醇甲醚醋酸酯等。 The invention synthesizes a flame retardant hardener, and the solvent used includes: benzene, toluene, xylene, dioxane, DMF, DMAC, methanol, ethanol, propanol, butanol, dipropylene glycol methyl ether, diethylene glycol Methyl ether, propylene glycol methyl ether, ethylene glycol methyl ether, propylene glycol methyl ether acetate, and the like.
本發明合成一種耐燃性硬化劑，其所使用之鹼性觸媒包括：氫氧化鈉、氫氧化鉀、氫氧化鎂、碳酸鈉、碳酸鉀、碳酸鈣、三級胺、氨等。 The present invention synthesizes a flame retardant hardener, and the alkaline catalyst used includes sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, tertiary amine, ammonia and the like.
本發明合成一種耐燃性硬化劑，其所使用之鹼酸性觸媒包括：鹽酸、硫酸、醋酸、草酸、檸檬酸、苯磺酸、甲基苯磺酸及 其它路易士酸等 The invention synthesizes a flame retardant hardener, and the alkali acid catalyst used therein comprises: hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, citric acid, benzenesulfonic acid, methylbenzenesulfonic acid and Other Lewis acid, etc.
本發明之目的在提供一種耐燃性硬化劑組成物，包括：(a)耐燃性硬化劑，其具有如式(一)所式之化學結構：
本發明之一種耐燃性硬化劑組成物之環氧樹脂，使用二個環氧基以上之多官能基環氧樹脂包括：酚醛型環氧樹脂、甲酚醛型環氧樹脂、雙酚A醛型環氧樹脂、四苯基縮水甘油醚基乙烷、三苯基縮水甘油醚基甲烷、三縮水甘油基對胺基苯酚、三縮水甘油基三聚異氰酸酯、四縮水甘油基二胺基二苯基甲烷、四縮水甘油基二甲苯二胺、四縮水甘油基1,3-雙氨基甲基環己烷三甲醇基丙烷三縮水甘油醚、丙三醇三縮水甘油醚、其它二個以上環氧基之環氧樹脂、二個以上環氧基之環氧樹脂稀釋劑等。 The epoxy resin of the flame-resistant hardener composition of the present invention, the polyfunctional epoxy resin using two epoxy groups or more includes: a phenolic epoxy resin, a cresol novolac epoxy resin, a bisphenol A aldehyde ring Oxygen resin, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl p-aminophenol, triglycidyl trimer isocyanate, tetraglycidyl diaminodiphenylmethane , tetraglycidyl xylene diamine, tetraglycidyl 1,3-diaminomethylcyclohexane trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, two or more other epoxy groups Epoxy resin, epoxy resin diluent of two or more epoxy groups, and the like.
本發明之一種耐燃性硬化劑組成物之環氧樹脂，使用含二個環氧基之環氧樹脂包括：雙酚A型縮水甘油醚、雙酚F型縮水甘油醚、雙酚S型縮水甘油醚、氫化雙酚A型縮水甘油醚、氫化雙酚A型縮水甘油醚、鄰苯二甲酸縮水甘油酯、海因環氧樹脂、醯亞胺環 氧樹脂、雙(2,3環氧基環戊基)醚、3,4環氧基-6-甲基環己基甲酸-3',4'-環氧基-6'-甲基環己基甲酯、乙烯基環己烯二環氧化合物、3,4環氧基環己基甲酸-3',4'-環氧基環己基甲酯、二異戊二烯二環氧化物、二丁二烯二環氧化物、己二酸二(3,4環氧基-6-甲基環己基甲酯)、二縮水甘油醚、聚乙醇二縮水甘油醚、聚丙醇二縮水甘油醚、聚丁醇二縮水甘油醚、丁醇二縮水甘油醚、二縮水甘油基苯胺、對苯二甲酸二縮水甘油酯、內次甲基四氫鄰苯二甲酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、四氫鄰苯二甲酸二縮水甘油酯、間苯二甲酸二縮水甘油酯、4,5環氧環己烷1,2-二甲酸二縮水甘油酯、鄰苯二辛酸二環氧丙酯、二氧化戊烯、二氧化雙環戊二烯多元醇醚、其它二個環氧基之環氧樹脂、二個環氧基之環氧樹脂稀釋劑等。 The epoxy resin of the flame-resistant hardener composition of the present invention uses an epoxy resin containing two epoxy groups including: bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol S glycidyl Ether, hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol A glycidyl ether, glycidyl phthalate, hydantoin epoxy resin, quinone imine epoxy resin, bis (2,3 epoxy ring) pentyl) ether, 3,4-epoxy-6-methylcyclohexyl carboxylate 3 ', 4' - epoxy-6 '- methyl cyclohexyl methacrylate, vinylcyclohexene diepoxide, 3,4 epoxycyclohexylcarboxylic acid-3 ' , 4' -epoxycyclohexylmethyl ester, diisoprene diepoxide, dibutadiene diepoxide, adipic acid di(3, 4-epoxy-6-methylcyclohexylmethyl ester), diglycidyl ether, polyglycol diglycidyl ether, polyglycol diglycidyl ether, polybutanol diglycidyl ether, butanol diglycidyl ether, two Glycidyl aniline, diglycidyl terephthalate, sec-methyltetrahydrophthalic acid diglycidyl ester, diglycidyl phthalate, dihydrophthalic acid condensed water Glyceryl ester, diglycidyl isophthalate, 4,5 epoxy cyclohexane 1,2-dicarboxylic acid diglycidyl ester, diglycidyl phthalate, pentylene oxide, dicyclopentane dioxide Diene polyol ether, other epoxy resin of two epoxy groups, epoxy resin diluent of two epoxy groups, and the like.
本發明之一種耐燃性硬化劑組成物之硬化促進劑包括已知之三級胺、四級銨鹽、咪唑類、金屬有機鹽、膦類化合物、三氟硼胺錯合物、酚類等。 The hardening accelerator of the flame-resistant hardener composition of the present invention includes known tertiary amines, quaternary ammonium salts, imidazoles, metal organic salts, phosphine compounds, trifluoroboramine complexes, phenols and the like.
本發明之一種耐燃性硬化劑組成物之共硬化劑包括已知之，酚醛樹脂、二氰二胺、馬林酸酐/苯乙烯共聚物、三嗪酚醛樹脂、苯并咢井(Benzoxazine)等。 The co-hardener of a flame-resistant hardener composition of the present invention includes known phenolic resins, dicyandiamide, malic anhydride/styrene copolymer, triazine phenolic resin, Benzoxazine, and the like.
本發明之目的在提供一種難耐燃性硬化劑組成物，其係用於製造黏合片、複合材料、積層板、印刷電路板、增厚法之基板、銅箔用之接著劑、預浸漬片等。 An object of the present invention is to provide a flame-resistant hardener composition for producing an adhesive sheet, a composite material, a laminate, a printed circuit board, a substrate for a thickening method, an adhesive for a copper foil, a prepreg, etc. .
將2-苯基-3,3-雙(4-羥苯基)苯幷吡咯酮393g(1mole)、24%甲醛水溶液287.5g(2.3mole)、三乙胺1.0g，置入裝有機械攪拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至70℃，反應5小時後加入500g丁醇，將溫度升至90℃，反應5小時溫度後逐步加熱至120℃共沸去除水份，再加入9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物432g(2mole)，將溫度升至180℃減壓脫除溶劑，可得到耐燃硬化劑A，測量其磷含量為7.27%，氮含量為1.64%，OH當量為426。 2-phenyl-3,3-bis(4-hydroxyphenyl)benzopyrrole 393g (1mole), 24% formaldehyde aqueous solution 287.5g (2.3mole), triethylamine 1.0g, placed with mechanical stirring , the condensation tube, the distillation receiver, the four-neck reaction flask of nitrogen, the temperature is raised to 70 ° C, after 5 hours of reaction, 500 g of butanol is added, the temperature is raised to 90 ° C, and the reaction is gradually heated to 120 ° C for 5 hours. The water is removed by boiling, and 432g (2mole) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, and the temperature is raised to 180 ° C to remove the solvent under reduced pressure to obtain flame-resistant hardening. Agent A was measured to have a phosphorus content of 7.27%, a nitrogen content of 1.64%, and an OH equivalent of 426.
將酚酞318g(1mole)、24%甲醛水溶液287.5g(2.3mole)、三乙胺1.0g，置入裝有機械攪拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至70℃，反應5小時後加入500g丁醇，將溫度升至90℃，反應5小時溫度後逐步加熱至120℃共沸去除水份，再加入9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物432g(2mole)，將溫度升至180℃減壓脫除溶劑，可得到耐燃硬化劑B，測量其磷含量為7.97%，OH當量為389。 Phenolphthalein 318g (1mole), 24% formaldehyde aqueous solution 287.5g (2.3mole), triethylamine 1.0g, placed in a four-port reaction flask equipped with mechanical stirring, condensation tube, distillation receiver, nitrogen, the temperature was raised to After reacting at 70 ° C for 5 hours, add 500 g of butanol, raise the temperature to 90 ° C, react for 5 hours, gradually heat to 120 ° C to azeotropically remove water, and then add 9,10-dihydro-9-oxa-10 - phosphaphenanthrene-10-oxide 432 g (2 mole), the temperature was raised to 180 ° C to remove the solvent under reduced pressure to obtain a flame-resistant hardener B, which was measured to have a phosphorus content of 7.97% and an OH equivalent of 389.
將2-氫-3,3-雙(4-羥苯基)苯幷吡咯酮317g(1mole)、24%甲醛水溶液375g(3.0mole)、三乙胺1.0g，置入裝有機械攪拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至70℃，反應5小時後加入500g丁醇，將溫度升至90℃，反應5小時溫度 後逐步加熱至120℃共沸去除水份，再加入9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物432g(2mole)，將溫度升至180℃減壓脫除溶劑，可得到耐燃硬化劑C，測量其磷含量為9.29%，氮含量為1.40%，OH當量為500。 Hydrate 2-hydro-3,3-bis(4-hydroxyphenyl)benzopyrrolidone 317g (1mole), 375g (3.0mole) of 24% aqueous formaldehyde solution, 1.0g of triethylamine, placed in mechanical stirring, condensation Tube, distillation receiver, nitrogen four-neck reaction flask, the temperature was raised to 70 ° C, after 5 hours of reaction, 500 g of butanol was added, the temperature was raised to 90 ° C, and the reaction was carried out for 5 hours. After gradually heating to 120 ° C azeotropic removal of water, and then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 432g (2mole), the temperature is raised to 180 ° C decompression In addition to the solvent, a flame-resistant hardener C was obtained, which was measured to have a phosphorus content of 9.29%, a nitrogen content of 1.40%, and an OH equivalent of 500.
將酚酞318g(1mole)、雙酚A 228g(1mole)、24%甲醛水溶液500g(4mole)、三乙胺1.0g，置入裝有機械攪拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至70℃，反應5小時後加入500g丁醇，將溫度升至90℃，反應5小時溫度後逐步加熱至120℃共沸去除水份，加入9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物432g(2mole)，將溫度升至150℃脫除溶劑，再加入三聚氰胺126g(1mole)將溫度升至180℃減壓脫除溶劑，可得到耐燃硬化劑D，測量其磷含量為5.89%，氮含量為7.29%，OH當量為228。 Phenolphthalein 318g (1mole), bisphenol A 228g (1mole), 24% formaldehyde aqueous solution 500g (4mole), triethylamine 1.0g, placed in a four-port reaction bottle equipped with mechanical stirring, condenser, distillation receiver, nitrogen In the middle, the temperature was raised to 70 ° C, and after reacting for 5 hours, 500 g of butanol was added, the temperature was raised to 90 ° C, and after reacting for 5 hours, the temperature was gradually heated to 120 ° C to azeotropically remove water, and 9,10-dihydro-9 was added. - oxa-10-phosphaphenanthrene-10-oxide 432g (2mole), the temperature is raised to 150 ° C to remove the solvent, and then added melamine 126g (1mole), the temperature is raised to 180 ° C, the solvent is removed under reduced pressure, can be obtained The flame retardant D was measured to have a phosphorus content of 5.89%, a nitrogen content of 7.29%, and an OH equivalent of 228.
將2-苯基-3,3-雙(4-羥苯基)苯幷吡咯酮393g(1mole)、雙酚F 200g(1mole)、24%甲醛水溶液750g(6mole)、三乙胺1.0g，置入裝有機械攪拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至70℃，反應5小時後加入500g丁醇，將溫度升至90℃，反應5小時溫度後逐步加熱至120℃共沸去除水份，加入9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物864g(4mole)，將溫度升至150℃脫除溶劑，再加入苯基胍胺187g(1mole)將溫度升至180℃減壓脫除溶劑，可得到耐燃硬化劑E，測量其磷含量為7.22%， 氮含量為4.90%，OH當量為429。 2-phenyl-3,3-bis(4-hydroxyphenyl)benzopyrrole 393g (1mole), bisphenol F 200g (1mole), 24% formaldehyde aqueous solution 750g (6mole), triethylamine 1.0g, Placed in a four-neck reaction flask equipped with mechanical stirring, condenser, distillation receiver, nitrogen, the temperature was raised to 70 ° C, after 5 hours of reaction, 500 g of butanol was added, the temperature was raised to 90 ° C, and the reaction was carried out for 5 hours. Gradually heat to 120 ° C azeotropic removal of water, add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 864g (4mole), the temperature is raised to 150 ° C to remove the solvent, and then 187 g (1 mole) of phenyl decylamine was added, and the temperature was raised to 180 ° C to remove the solvent under reduced pressure to obtain a flame-resistant hardener E, and the phosphorus content was measured to be 7.22%. The nitrogen content was 4.90% and the OH equivalent was 429.
將2-氫基-3,3-雙(4-羥苯基)苯幷吡咯酮393g(1mole)、9,9-雙(4-羥苯基)芴350g(1mole)、24%甲醛水溶液1000g(8mole)、三乙胺1.0g，置入裝有機械攪拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至70℃，反應5小時後加入500g丁醇，將溫度升至90℃，反應5小時溫度後逐步加熱至120℃共沸去除水份，加入9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物1080g(5mole)，將溫度升至150℃脫除溶劑，再加入甲基胍胺125g(1mole)將溫度升至180℃減壓脫除溶劑，可得到耐燃硬化劑F，測量其磷含量為7.56%，氮含量為3.41%，OH當量為512。 2-Hydroxy-3,3-bis(4-hydroxyphenyl)benzopyrrole 393g (1mole), 9,9-bis(4-hydroxyphenyl)fluorene 350g (1mole), 24% formaldehyde aqueous solution 1000g (8mole), triethylamine 1.0g, placed in a four-neck reaction flask equipped with mechanical stirring, condenser, distillation receiver, nitrogen, the temperature was raised to 70 ° C, after 5 hours of reaction, 500 g of butanol was added, the temperature was Raise to 90 ° C, react for 5 hours, gradually heat to 120 ° C azeotropic removal of water, add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 1080g (5mole), will The temperature was raised to 150 ° C to remove the solvent, and then added with methyl guanamine 125 g (1 mole). The temperature was raised to 180 ° C to remove the solvent under reduced pressure to obtain a flame retardant F, which was measured to have a phosphorus content of 7.56% and a nitrogen content of 3.41. %, OH equivalent is 512.
將雙酚A 228g(1mole)、24%甲醛水溶液287.5g(2.3mole)、三乙胺1.0g，置入裝有機械攪拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至70℃，反應5小時後加入500g丁醇，將溫度升至90℃，反應5小時溫度後逐步加熱至120℃共沸去除水份，再加入9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物432g(2mole)，將溫度升至180℃減壓脫除溶劑，可得到耐燃硬化劑G，測量其磷含量為9.01%，OH當量為344。 The bisphenol A 228g (1mole), 24% formaldehyde aqueous solution 287.5g (2.3mole), triethylamine 1.0g, placed in a four-port reaction bottle equipped with mechanical stirring, condensation tube, distillation receiver, nitrogen, the temperature Raise to 70 ° C, after 5 hours of reaction, add 500 g of butanol, raise the temperature to 90 ° C, react for 5 hours, then gradually heat to 120 ° C to azeotropically remove water, then add 9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide 432 g (2 mole), the temperature was raised to 180 ° C to remove the solvent under reduced pressure to obtain a flame-resistant hardener G, which was measured to have a phosphorus content of 9.01% and an OH equivalent of 344.
將實施例1~6及比較例1之耐燃硬化劑A~G、N-680(DIC/環氧樹脂/環氧當量=212)、酚醛樹脂(OH當量=105)、促進劑2E4MZ(2- 乙基-四甲基咪唑)、以丁酮200g溶解均勻，靜置12小時，調製成樹脂清漆，以習知方法製備積層板，該法係將7628玻璃纖維布含浸上述清漆樹脂液，然後於170℃(含浸機溫度)，乾燥1~3分鐘，藉由調整控制乾燥時間得預浸半固化片，最後將8片半固化片層層相疊於兩片35μum厚之銅箔間，在25kg/cm2壓力下，其控制升溫程式為溫度85℃時間30min→溫度140℃時間10min→溫度220℃時間120min→冷壓降溫至80℃，經熱冷壓後即可得到積層壓合板。而可得到1.6mm厚之銅箔基板，樹脂含量係在40-45%的範圍內，然後以DSC測試層合物的玻璃轉移溫度(Tg1)、以TGA測試層合物的熱分解溫度及UL-94難燃性；將預浸半固化片，放置於溫度20℃，相對濕度80%之環境下7日，再將8片半固化片層層相疊於兩片35μum厚之銅箔間，在25kg/cm2壓力下，其控制升溫程式為溫度85℃時間30min→溫度140℃時間10min→溫度220℃時間120min→冷壓降溫至80℃，經熱冷壓後即可得到積層壓合板。而可得到1.6mm厚之銅箔基板，樹脂含量係在40-45%的範圍內，然後以DSC測試層合物的玻璃轉移溫度(Tg2)，其結果如表一所示。 The flame-resistant hardeners A to G, N-680 (DIC/epoxy resin/epoxy equivalent = 212), phenolic resin (OH equivalent = 105), and accelerator 2E4MZ (2-) of Examples 1 to 6 and Comparative Example 1 were used. Ethyl-tetramethylimidazole) was dissolved in 200 g of butanone and allowed to stand for 12 hours to prepare a resin varnish. A laminate was prepared by a conventional method. The method was carried out by impregnating 7628 glass fiber cloth with the above varnish resin liquid, and then 170 ° C (the temperature of the impregnation machine), drying for 1 to 3 minutes, pre-impregnated prepreg by adjusting the drying time, and finally stacking 8 prepreg layers between two 35μum thick copper foils at a pressure of 25kg/cm 2 Next, the temperature control program is controlled to a temperature of 85 ° C for 30 min → temperature of 140 ° C for 10 min → temperature of 220 ° C for 120 min → cold pressure to 80 ° C, after hot and cold pressing to obtain a laminate. A 1.6 mm thick copper foil substrate is obtained, the resin content is in the range of 40-45%, and then the glass transition temperature (Tg1) of the laminate is tested by DSC, and the thermal decomposition temperature and UL of the laminate are tested by TGA. -94 flame retardant; prepreg prepreg, placed in a temperature of 20 ° C, relative humidity of 80% of the environment for 7 days, and then stack 8 pieces of prepreg layer between two pieces of 35μum thick copper foil, at 25kg / cm Under the pressure of 2 , the temperature control program is controlled by the temperature of 85 ° C for 30 min, the temperature is 140 ° C for 10 min, the temperature is 220 ° C for 120 min, the cold pressure is lowered to 80 ° C, and the laminate is obtained by hot cold pressing. A 1.6 mm thick copper foil substrate was obtained, and the resin content was in the range of 40 to 45%. Then, the glass transition temperature (Tg2) of the laminate was measured by DSC, and the results are shown in Table 1.
由表一可知實施例1~6所合成之耐燃硬化劑A~F配製成實施例7~12之硬化物表現出耐燃性(UL-94/V-0)，磷含量需求為1.62%~2.02%，低於已知耐燃硬化劑G之磷含量需求2.6%；實施例7~12△Tg為0~1，實施例13~14△Tg為10~11，表示本發明之耐燃硬化劑組成物半固化物之經時安定性優於傳統已知者，適合用於用於製造黏合片、複合材料、積層板、印刷電路板、增厚法之基板、銅箔用之接著劑、預浸漬片等。 It can be seen from Table 1 that the fire-resistant hardeners A to F synthesized in Examples 1 to 6 are formulated into the cured products of Examples 7 to 12 to exhibit flame resistance (UL-94/V-0), and the phosphorus content requirement is 1.62%. 2.02%, lower than the phosphorus content requirement of known flame retardant G. 2.6%; Examples 7-12 △Tg is 0~1, and Examples 13-14 △Tg are 10-11, indicating the composition of the flame retardant of the present invention The semi-cured material has better stability over time than conventional ones, and is suitable for use in the manufacture of adhesive sheets, composite materials, laminated boards, printed circuit boards, substrates for thickening methods, adhesives for copper foils, pre-impregnation. Film and so on.
本發明已經配合上述具體實施例、比較例描述，熟悉本項技藝人士將可基於以上描述作出多種變化，不因此而限制本發明之申請專利範圍。 The present invention has been described in connection with the foregoing specific embodiments and comparative examples, and those skilled in the art can make various changes based on the above description, and do not limit the scope of the patent application of the present invention.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100117823A TWI480365B (en) | 2011-05-20 | 2011-05-20 | Flame retardant hardener and flame retardant hardene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100117823A TWI480365B (en) | 2011-05-20 | 2011-05-20 | Flame retardant hardener and flame retardant hardene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201247853A TW201247853A (en) | 2012-12-01 |
| TWI480365B true TWI480365B (en) | 2015-04-11 |
Family
ID=48138538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100117823A TWI480365B (en) | 2011-05-20 | 2011-05-20 | Flame retardant hardener and flame retardant hardene composition |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI480365B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI647265B (en) | 2018-02-05 | 2019-01-11 | Taiwan Union Technology Corporation | Resin composition, and prepreg, metal foil laminate, and printed circuit board prepared using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0539345A (en) * | 1991-08-02 | 1993-02-19 | Hokko Chem Ind Co Ltd | Phosphorus-containing epoxy resin |
| TW498084B (en) * | 2000-07-19 | 2002-08-11 | Chang Chun Plastics Co Ltd | Flame-retardant resin and flame retardant composition containing the same |
| TW593526B (en) * | 2001-09-20 | 2004-06-21 | Wangsuen Su Jen | Phosphorus group containing flame retardant hardener, advanced epoxy resins and cured epoxy resins thereof |
| US20100234495A1 (en) * | 2007-04-03 | 2010-09-16 | Ciba Corporation | Dopo flame retardant compositions |
-
2011
- 2011-05-20 TW TW100117823A patent/TWI480365B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0539345A (en) * | 1991-08-02 | 1993-02-19 | Hokko Chem Ind Co Ltd | Phosphorus-containing epoxy resin |
| TW498084B (en) * | 2000-07-19 | 2002-08-11 | Chang Chun Plastics Co Ltd | Flame-retardant resin and flame retardant composition containing the same |
| TW593526B (en) * | 2001-09-20 | 2004-06-21 | Wangsuen Su Jen | Phosphorus group containing flame retardant hardener, advanced epoxy resins and cured epoxy resins thereof |
| US20100234495A1 (en) * | 2007-04-03 | 2010-09-16 | Ciba Corporation | Dopo flame retardant compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201247853A (en) | 2012-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI753136B (en) | Phosphorus-containing phenolic compounds, phosphorus-containing epoxy resins, curable resin compositions thereof or epoxy resin compositions and cured products thereof | |
| JP6487891B2 (en) | Phosphorus-containing compound and method for producing the same | |
| WO2011152412A1 (en) | Epoxy resin composition and pre-preg, support-provided resin film, metallic foil clad laminate plate and multilayer printed circuit board utilizing said composition | |
| EP2985300B1 (en) | Phosphor-containing phenol formaldehyde resin compound and flame-retardant epoxy resin hardener made from thereof | |
| KR20150058335A (en) | Epoxy resin composition, and, prepreg and copper clad laminate manufactured using the composition | |
| EP2682398B1 (en) | Phosphorus-atom-containing oligomer composition, curable resin composition, substance resulting from curing same, and printed circuit board | |
| TWI585098B (en) | Cyanide-containing phosphazene compound, preparation method and use thereof | |
| JP2017088600A5 (en) | ||
| JP5240516B2 (en) | Epoxy resin composition, cured product thereof, and build-up film insulating material | |
| TW201739832A (en) | Oxazine resin composition and cured product thereof | |
| WO2015184652A1 (en) | Zero-halogen resin composition and prepreg and printed circuit laminate using same | |
| JP2010077343A (en) | Epoxy resin composition, cured product of the same, and buildup film insulating material | |
| JP2020015823A (en) | Epoxy resin composition, prepreg, laminate, and printed wiring board | |
| JP7387413B2 (en) | Epoxy resin composition, laminates and printed circuit boards using the same | |
| TWI480365B (en) | Flame retardant hardener and flame retardant hardene composition | |
| JP7368551B2 (en) | Method for producing epoxy resin composition and method for using biphenylaralkyl phenolic resin | |
| JP6947520B2 (en) | A method for producing an organic phosphorus compound, a curable resin composition containing an organic phosphorus compound, a cured product thereof, and an organic phosphorus compound. | |
| JP5866806B2 (en) | Epoxy resin composition, prepreg using this epoxy resin composition, resin film with support, metal foil-clad laminate and multilayer printed wiring board | |
| JP6304294B2 (en) | Epoxy resin composition, prepreg using this epoxy resin composition, resin film with support, metal foil-clad laminate and multilayer printed wiring board | |
| JP6369892B2 (en) | Phosphorus-containing flame retardant epoxy resin | |
| JP7211744B2 (en) | Epoxy resin composition and cured product thereof | |
| JP5307041B2 (en) | Thermosetting resin composition, prepreg using the same, and laminate for electric wiring board | |
| EP2374828B1 (en) | Preparation of a low dielectric brominated resin with a symmetric or saturated heterocyclic aliphatic molecular structure and composition comprising said resin | |
| JP2015224323A (en) | Phosphorus-containing flame-retardant phenol resin | |
| TWI403532B (en) | Flame retardant hardener and flame retardant hardener composition |